Water-soluble organic dyestuffs



United States Patent 3,158,596 WATER-SGLUBLE JRGANEC DYESTUFFS Kari Seitz, Allschwii, and Henri Riat, Ariesheirn, Switzerlmd, iguors to fiba Limited, Basel, Switzerland, :1 $wiss firm No Drawing. Filed Sept. 25, 1%58, Ser. No. 763,168 (liaims priority, appiication Switzeriand Sept. 27, 1957 2 (Jiahns. (Ci. 269-163) This invention provides valuable new Water-soluble organic dyestuifs which contain at least one group imparting solubility in water and the radical of a halogenated aliphatic unsaturated dicarboxylic acid of low molecular weight bound to the dyestuli molecule through one of its two CO groups.

As radicals of halogenated dicarboxylic acids there may be mentioned above all the radicals of the formulae COOH These radicals may be bound through the CO group to an aromatic nucleus of the dyestuff molecule directly or advantageously through a nitrogen atom. The nitrogen atom may contain as a further substituent an aliphatic, cycloaliphatic araliphatic or aromatic radical. Especially valuable are those dyestuffs of the present invention which contain at least one group of the formula in which one of the two Xs represents a chlorine atom and the other X a hydrogen atom, and n is a Whole number advantageously 1.

In addition to a group of the aforesaid kind, which may be bound through an SO group or an alkylene radical, or advantageously, to an aromatic ring of the dyestufi molecule, the dyestuffs of the invention contain at least one group imparting solubility in water, for example, a sulfonic acid amide group which may be acylated, a sulfone group or advantageously at least one strongly acid group imparting solubility in water, such as a carboxylic acid or sulfonic acid group. They may also contain further substituents, especially those not imparting solubility in water, such as halogen atoms or nitro, acylamino, alkyl or alkoxy groups.

The group imparting solubility in water and the group derived from a halogenated aliphatic dicarboxylic acid may be distributed in the dyestufi molecule in any manner. Thus a group of each kind may be present in a single component or one dyestufi component may contain the group imparting solubility in water and the other component may contain the group of the Formula 1.

The dyestufis can be made from dyestufi components which themselves contain the aforesaid halogenated carboxyalkene radial. Such dyestufi; components can be made by methods in themselves known, for example, by acylating a suitable compound with a halide or more especially an anhydride of a halogenated unsaturated aliphatic dicarboxylic acid.

Suitable compounds for this purpose are, for example, those which contain an easily acylatable amino group, for example, a monoalkylarnino group or a primary amino group, a nitro group or a less easily acylatable primary amino group, and which compounds, after the acylation and, when necessary reduction of the nitro group, serve as diazocomponents. The coupling components may likewise contain an easily or less easily acylatable amino group causing coupling or a nitro group or a hydroxyl group causing coupling. As less easily acylatable amino groups there may be mentioned more especially those in a position vicinal to an acid group, for example, a sulfonic acid group. Amino-hydroxy-compounds are acylated in such manner that esterification of the hydroxyl group is avoided, for which purpose, as is known, a non-alkaline reaction medium is suitable. The nitrocompounds are reduced to the amines after the acylation.

Instead of introducing the aforesaid halogenated wcarboxy-aikene radical into a dyestufi component before the dyestufi is made, it may likewise be introduced into the finished dyestuiI'. Thus, valuable dyestuffs are obtained by the acylation with chloromaleic anhydride of dyestuffs which contain an acylatable amino group, that is to say an at most secondary or preferably a free amino group.

As soluble organic dyestuffs there may be used dyestuffs belong to a very Wide variety of classes, for example, stilbene dyestuffs, azine dyestuffs, dioxazine dyestuffs, Xanthone dyestuffs, thioxanthone dyestufis, acid phthalocyanine dyestuffs and above all acid anthraquinone dyestuffs and especially azo-dyestufis, including metal-free and metalliferous monoand poly-aZo-dyestuiis. Especially good results are obtained with soluble azo-dyestutfs which possess no pronounced aiiinity for cotton.

As examples of dyestuffs containing acylatable amino groups, which can be acylated according to the present invention with halogenornaleic anhydride, and especially chloromaleic anhydride, may be mentioned the following: Aminoazo dyestufis obtainable by hydrolysing acylaminoazo dyestuffs, or by reduction of the nitro group of azo dyestuiis containing nitro groups, by coupling diazotized aromatic amines with coupling components containing acylatable amino groups, such as meta-acylaminoaminobenzenes, l-aminophenyl-3-methylor 3-carboxy- S-pyrazolone, aminonaphtholsulfonic acid or the like;

amino dyestuifs of the anthraquinone series such as l-amino-4-(3'- or -4'-arninophenylamino)anthraquinone- 2-sulfonic acid,

l-arni-noi- 4-'-aminophenylarnino -anthraquinone-2'- or -3'-sulfonic acid,

l-amino-4-(4--arninophenylan1ino) anthraquinone-Z 2- or 2: 3'-disulfonic acid,

1-amino-4- 3-aminophenylamino) anthraquinone-Z 4'-disulfonic acid,

l-amino-4- (4'-aminophenylamino anthraquinone-Z 3 5-,

-2:3':6-, -2:3:7- or -2:3':8-trisulfonic acid,

1-an1ino-4- 4-arninophenylamino anthraquinone-Z 2' 5- trisulfonic acid,

l-amino-4- 3 aminophenylamino) anthraquinone-Z 2' 8- trisulfonic acid,

furthermore l 5-dihydroxy-4: B-diaminoanthraquinone- 2:6-disulfonic acid,

1:4- or l:S-diaminoanthraquinone2-sulfonic acid,

4-, 5- or S-amino-l-acylaminoanthraquinones (obtained by acylating a l-aminoanthraquinone that contains a nitro group in the 4-, 5- or 8-position, by mean of a sulfoor disulfo-benzoic acid halide and subsequent reduction of the nitro group to an amino group), aminodibenzantln'onesulfonic acid and aminc -isodibenzanthronesulfonic acids (obtained by introducing two sulfonic acid groups into amino-dibenzanthrone or into amino-isodibenzanthrone), furthermore, there are obtained, for example, from 1 mol of a trior tetrasulfonic acid chloride of a colored anthraquinone derivative, or from 1 mol of a phthalocyanine trior tetrasulfonic acid chloride, by partial amidation with 1 mol of a diamine, for example with 1 mol of a diaminobenzenesulfonic acid or of a monoacyl derivative thereof, very valuable dyestuffs suitable as starting materials in the present process which, after hydrolysis of the unreacted sulfonic acid chloride groups The dyeings obtained with the dyestuffs of the invention on wool and on cellulosic fibers are as a rule distinguished by the purity of their tints, by good fastness to light and above all by outstmding fastness to washing.

and of any acylarnino group present, contain an acylat- 5 The following exarnples illustrate the invention. Unable amino group, which dyestuffs are capable of reless otherwise indicated, parts and percentages are by acting according to the invention with chloromaleic acid weight. chloride or anhydride. Example 1 The acylation according to the invention of such dye stuifs containing an acylatable amino group with a halo- 10'44 Parts of the dyestufl of the formula genomaleic acid anhydride is advantageously performed CH? in the presence of an acid acceptor such as sodium acei tate, sodium hydroxide or sodium carbonate and under N OH S|O3H relatively mild conditions, for example in an organic \N/ solvent, or at a relatively low temperature in an aqueous medium. The chlorornaleic anhydride may be replaced C1 with an appropriate dillalide of chloromaleic or chlorofurnaric acid, provided it is ensured that only one of the C1 two acid halide groups reacts with the amino g1 cup of the I dyestuff used, and after formation of the dyestuff the sec- SO H ond acid halide group is hydrolysed to the carboxyl are neutralized in 300 parts of water with sodium cargroup. bonate, and 6.56 parts of anhydrous sodium acetate are The dyestuffs obtained by the process described above added. The solution is cooled to 0 to 5 C., a solution are new. They are suitable for dyeing and printing a of 5.3 parts of chloromaleic anhydride in parts of very 'wide variety of materials such as wool, silk or 2 5 acetone is run in, and the mixture is stirred until cornsuperpolyarnide fibers, and more especially polyhydroxyiplete acylation of the amino group has been achieved. ated fibrous materials, such as cellulosic materials, which The solution is then adjusted to pH=9 with sodium carmay be either synthetic (e.g. or regenerated cellulose) or bonate, and the dyestuff formed is salted out with sodium natural materials such as cellulose, linen or above all chloride, filtered off and dried in vacuo at 70 to 75 C. cotton. They are suitable for dyeing by the so-called The dyestuff obtained in this manner dyes cotton direct-dyeing method and also for printing and pad-dyeing, golden yellow tints of very good fastness to washing more especially from an alkaline aqueous solution and light. which may be strongly stalted, if desired-for example by Acylation of the aminoazo dyestufis in column I of the process according to which the dyestufi is fixed on the following table with chlorornaleic anhydride as dethe material to be dyed by a heat treatment, for example scribed in Example 1 yields further dyestutls which dye by steaming, in the presence of an alkali. cotton the tints listed in column II.

I II

GHSNN=NQNH, Yellow.

-N=N cn Greenish yellow. sonar no N r 3 N=N-NH1 Bluish red. OH S0 11 4 N=N' N=N NH Yellowish brown.

SOgH

503K (IJCH3 5 N= Q-NEH Yellow.

described in Example 1.

I II

6 N=N NH1 D0.

NHGOCH S0311 SIOSH 7 -N=NONH2 Do.

I 503E s o H mm 8 1 -O-Nm Yelloworange. $113 I SO H s oarr 9 H3 N=N-C Greenish n 7 yellow. N OH 1 :11

HO;S

Example 2 Example 4 5.18 parts of the dyestufi? of the formula pans of the dyestufi of the formula OH OH OH NHz I I I NHz-C -N=N I H0aS NH1 1103s HOaS SO;H I

Example 3 10 parts of the copper complex of the formula N=N I O Hols-@413, p

. are reacted with 5.3 parts of chloromaleic anhydride as The acylated dyestuff is salted out with potassium chloride and filtered off.

The dyestuif obtained in this manner dyes cotton ruby red tints. 7 5

are neutralized in parts of Water with sodium carbonate. 2.4 parts by volume of 10 N sodium hydroxide solution and 24 parts by volume of a chromium sodium salicylate solution containing in 100 parts by volume of Water 2.8 parts of chromium are added, and the mixture is refluxed for 3 hours. The solution of the resulting 1:2- chromium complex compound is allowed to cool, neutralized with hydrochloric acid and diluted with Water to 300 parts by volume. This solution is treated with 6.56 of anhydrous sodium acetate and cooled to O-5 C. Addition of 5.3 parts of chloromaleic anhydride acylates the amino group completely. The solution is then adjusted to pH=9 with sodium carbonate, and the dyestufi is precipitated With sodium chloride and filtered 01f.

The dyestutr obtained in this manner dyes cotton reddish blue tints.

Example 5 8.'78 parts of the dyestufi of the formula HOgS- NH2 are neutralized in 100 parts of water with sodium carbonate. 2.4 parts by volume of 10 N sodium hydroxide solution and 62 parts by volume of a cobalt sulfate solution of strength are added, and the mixture is heated for /2 hour at 7580 C. The solution of the 1:2-cobalt complex formed is allowed to cool, adjusted to pH=7 and then reacted with chloromaleic anhydride as described in Example 4.

The dyestufi obtained in this manner dyes cotton violetbrown tints.

Example 6 7.78 parts of the dyestulf of the formula I NHg are converted into the 1:2-chrornium complex as described in Example 4 and acylated with chloromaleic an- II o hLFQNIn are dissolved together with 5.3 parts of sodium carbonate in 400 parts of water. The solution is cooled to OS C. and 5.3 parts of chloromaleic anhydride are added. One hour later the solution is adjusted to pH: with sodium carbonate. Addition of 100 parts of sodium chloride precipitates the acylated dyestuff.

The dyestuif obtained in this manner dyes cotton greenish blue tints.

Example 8 By using 7.27 parts of the dyestuff of the formula (prepared by the known method, for example as described in U.S. Patent No. 2,763,641, patented September 18, 1956, by Karl Seitz et a1.) and acylating the two amino groups with chlorornaleic anhydride as described in Example 2, a dyestufif is obtained which dyes cotton blue tints.

Example 9 6.4 parts of the condensation product from 1 mol of 2:S-diaminobenzene-l-sulfonic acid and 1 mol of chlorornaleic anhydride (prepared as described below) are neutralized in 250 parts of water with sodium carbonate, and diazotized at 05 C. in the known manner by adding 6 parts of hydrochloric acid of 30% strength and 10 parts of 2 N sodium nitrite solution.

By coupling with 5-(2':5-dichlorophenyl) 3 -methylpyrazolone-4-sulfonic acid in a medium rendered alka- I II (1) 1-Acetoacetylamino-2 methoxybenzene Greenish yellow. Barbiturie acid D0. 1-Naphthol-3:6-disulionic acid Red.

2-Aeotylamino-5-hydroxynaphthalene-T- Scarlet sulfonic acid. red. 1-Benzoylamino-8-hydroxynaphthalene-3 :6- Violet.

disulfonic acid. 1-Hydroxynaphthalene-t-sulionic acid Red.

The above mentioned condensation product from 2:5- diaminobenzene-l-sulfonic acid and chloromaleic anhydride can be prepared thus:

18.8 parts of 2:5-diaminobenzene-l-sulfonic acid are dissolved in 400 parts of water, neutralized and then mixed with 30 parts of anhydrous sodium acetate. To the solution are added 14.57 parts of chloromaleic anhydride in 25 parts of acetone. On completion of the reaction the solution is acidified with hydrochloric acid, and the precipitated reaction product is suctioned off and washed with saturated sodium chloride solution.

Example 10 A neutral solution of 18.8 parts of 2:4-diaminobenzene- 1-sulfonic acid in 300 parts of water is cooled to 05 C. and mixed with a solution of 13.25 parts of chloromaleic anhydride in 25 parts of acetone. The solution is readjusted to pH=7 by the dropwise addition of N-sodium hydroxide solution.

The solution of the resulting condensation product is diazotized in the known manner with 30 parts by volume of hydrochloric acid of 30% strength and 25 parts by volume of 4 N sodium nitrite solution.

Coupling with 1-benzoylamino-S-hydroxynaphthalene- 3:6-disulfonic acid in a medium rendered alkaline with bicarbonate produces a dyestuff which dyes cotton bluish red tints.

When the aforesaid l-benzoylamino 8 hydroxynaphthalene-3:6-disulfonic acid is replaced with 5-(2:5'-dichlorophenyl) 3 methylpyrazolone 4'-sulfonic acid or with barbituric acid as coupling component, dyestuffs are obtained which dye cotton greenish yellow tints.

By using 6-ureido-1-hydroxynaphthalene-3-sulfuric acid as coupling component there is obtained a dyestuff that dyes cotton pure orange tints that are fast to Washing.

Example 11 31.9 parts of 1:8-aminonaphthol 3:6 -disulfonic acid are dissolved in 500 parts of water, neutralized with sodium hydroxide and mixed with 30 parts of anhydrous sodium acetate. 14.57 parts of chloromaleic anhydride in 25 parts of acetone are added at room temperature. When a free amino group can no longer be detected, another 30 parts of sodium acetate are added, and the diazo compound prepared from 17.3 parts of Z-aminobenzene-l-sulfonic acid is run in.

The dyestuff obtained in this manner dyes cotton red tints.

By using, instead of Z-aminobenzene-l-sulfonic acid, 3- arninobenzene-l-sulfonic acid or 4-aminobenzene-1-sulfonic acid, there are obtained dyestuffs which yield somewhat more bluish tints.

In this example there may be used, instead of chloromaleic anhydride, the corresponding quantity of brornomaleic anhydride. A dyestuff having very similar properties is obtained.

5 Example 12 23.9 parts of 2-arnino-5-hydroxynaphthalene-7-sulfonic acid in 500 parts of water are neutralized with sodium hydroxide and mixed with 30 parts of sodium acetate. The solution is cooled to 5 C. and 14.57 parts of chloromaleic anhydride are added. When the amino group has been completely acylated, 40 parts of sodium bicarbonate are added to the solution and coupling with the diazo compound from 173 parts of 2-amino-benzene-1-sulfonic acid is performed.

A dyestuif is obtained which dyes cotton orange tints that are fast to washing.

By using 5-acetylamino-2-aminobenzene-l-sulfonic acid as diazo-compound, a dyestufl? is obtained which dyes cotton scarlet tints.

By using Z-aminonaphthalene-S:7-disulfonic acid as diazo-component a dyestuif is obtained that dyes cotton red-orange tints.

By using 1-amino-diphenyl-2-sulfonic acid a dye-stuff having similar properties is obtained.

Example 13 12.65 parts of 2-methylamino-5-hydroxynaphthalene-7- sulfonic acid in 100 parts of water are neutralized with sodium carbonate and mixed with 15.9 parts of chloromaleic anhydride. The solution is rendered neutral again by the dropwise addition of N-sodium hydroxide solution. 15 parts of sodium bicarbonate are added, and the diazonium salt solution prepared from 8.65 parts of Z-aminobenzene-l-sulfonic acid is run in.

The dyestutf obtained in this manner dyes cotton orange tints.

In this example the chloromaleic anhydride may be replaced by the corresponding quantity of bromomaleic anhydride, and a dyestufi having similar properties is obtained.

Example 14 2 parts of the dyestufi obtained as described in Example 7 are mixed with parts of urea, dissolved in 26 parts of water, and then stirred into 50 parts of an alginate thickening of 4% strength. 2 parts of sodium carbonate are added, and the resulting printing paste is used for printing a cotton fabric on a roller printing machine.

The fabric printed in this manner is dried, steamed for 8 minutes at 100 or 101 C., rinsed, soaped at the boil for 15 minutes in a solution of 0.3% strength of a nonionio detergent, rinsed and dried.

A blue print is obtained which is fixed fast to boiling. By using a fabric of staple fibers of regenerated cellulose, instead of a cotton fabric, a similarly good result is achieved.

Example 15 3 parts of the dyestuff obtained as described in Exarrn pic 11 are dissolved in 100 parts of water at 50 C. A cotton fabric is impregnated with the resulting solution, and dried. The fabric is then impregnated with a solution at 20 C. containing, per liter, 10 grams of sodium hydroxide and 300 grams of sodium chloride, the fabric is then squeezed until it retains of its Weight of the solution, then steamed for 60 seconds at 110' C., rinsed, treated in a sodium bicarbonate solution of 0.5% strength, rinsed, soaped for hour in a solution of 0.3% strength of a non-ionic detergent at the boil, rinsed and dried. There is obtained a red dyeing fixed fast to boiling.

What is claimed is:

1. A water-soluble monoazo dyestuft which contains at least one sulfonic acid group and corresponds to the formula wherein A represents 3-methyl-5-pyrazolonyl bound in its 4-position to the azo linkage, one of the two Xs is a chlo rine atom and the other X is a hydrogen atom.

2. The dyestuif wh ch in its free acid state corresponds to the formula l SOaH wherein one of the two Xs is a chlorine atom and the other X is a hydrogen atom.

References Cited in the file of this patent UNITED STATES PATENTS 901,675 Boniger Oct. 20, 1908 2,155,001 Schmid Apr. 18, 1939. 2,195,784 Schmid Apr. 2, 1940 2,195,787 Schmid Apr. 2, 1940 2,794,032 Frey et a1. May 28, 1957 FOREIGN PATENTS 654,849 Germany Dec. 31, 1937 209,973 Switzerland Aug. 16, 1940 216,416 Switzerland Dec. 1, 1941 220,120 Switzerland June 16, 1942 

1. A WATER-SOLUBLE MONOAZO DYESTUFF WHICH CONTAINS AT LEAST ONE SULFONIC ACID GROUP AND CORRESPONDS TO THE FORMULA 